EP2791985B1 - Procédé permettant d'insérer ou de disperser des particules présentant des propriétés piézoélectriques à l'intérieur d'une couche - Google Patents

Procédé permettant d'insérer ou de disperser des particules présentant des propriétés piézoélectriques à l'intérieur d'une couche Download PDF

Info

Publication number
EP2791985B1
EP2791985B1 EP12797975.5A EP12797975A EP2791985B1 EP 2791985 B1 EP2791985 B1 EP 2791985B1 EP 12797975 A EP12797975 A EP 12797975A EP 2791985 B1 EP2791985 B1 EP 2791985B1
Authority
EP
European Patent Office
Prior art keywords
substrate
particles
layer
piezoelectric properties
quartz
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP12797975.5A
Other languages
German (de)
English (en)
Other versions
EP2791985A2 (fr
Inventor
Giorgio Eberle
Fabio Cappelli
Giuseppe PARONETTO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SPF Logica Srl
Original Assignee
SPF Logica Srl
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/IB2011/054507 external-priority patent/WO2012137045A1/fr
Priority claimed from PCT/IB2011/055194 external-priority patent/WO2012137048A1/fr
Application filed by SPF Logica Srl filed Critical SPF Logica Srl
Publication of EP2791985A2 publication Critical patent/EP2791985A2/fr
Application granted granted Critical
Publication of EP2791985B1 publication Critical patent/EP2791985B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/092—Forming composite materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L49/00—Compositions of homopolymers or copolymers of compounds having one or more carbon-to-carbon triple bonds; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
    • H05K2203/107—Using laser light
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12181—Composite powder [e.g., coated, etc.]

Definitions

  • the invention relates to a process or method for inserting or dispersing particles with piezoelectric properties, e.g. quartz particles, within a layer or substrate (preferably containing polarisable polymers) modifiable by an electromagnetic field to vary its electrical resistivity, from an insulator to a conductor or vice versa.
  • the invention also relates to the substrate obtained.
  • a substrate or paint polarisable for example by means of laser wherein some quartz is dispersed so as to also confer piezoelectric properties to the paint.
  • the invention sets out to solve this problem by the method defined in claim 1.
  • quartz When using quartz, it is advantageous to disperse in a matrix or substrate, preferably of solvent, sintered material containing quartz, known as "loaded quartz", that is provided with micro-electrodes, preferably metallic, to collect or send electric charges.
  • a process for loading quartz involves sublimating two conductor sheets above and below a layer of quartz at high temperature (about 700°C), sintering it at 1000°C and then cooling to about 200°C to then expose it to an electric field of about 3000V/cm so as to position all the quartz particles with the electrodes parallel and alongside each other.
  • a sandwich structure of oriented quartz placed between two conductor sheets results.
  • such sandwich is ground to form particles of quartz P (see Fig. 1 ) small as desired which each have two electrodes E.
  • the particles P are then dispersed in the substrate.
  • the quartz alone is really just an example of embodiment for the piezoelectric component of the particle. Any material with piezoelectric properties can replace the quartz. In particular it proved advantageous to use particles with PZT inside, since its Pb and Ti components act as counter-electrode to the component of quartz inside the PZT.
  • Fig. 1 shows for instance particles of oriented quartz compared to each other.
  • the quartz or PZT generates charge pulses following a pulsating force or load
  • the maximum energy yield is only achieved if the quartz or PZT is oriented parallel to the direction of the pulsating force. That is to say that the micro-electrodes of each particle of quartz or PZT should align with the line of action of the force, so as to receive the maximum component thereof.
  • each application may require different orientations.
  • the quartzes or PZT should preferably be inclined relative to the orthogonal to the road surface towards the incoming vehicle. Only this way the component resulting from the movement impressed on the substrate is exploited.
  • the sintering technique described above may at most produce (see Fig. 1 , left) quartz Q dispersed in a substrate 10 which has two electrodes Ewhose axis X is oriented substantially orthogonal to the main surface S of the substrate 10 (parallel to the line H orthogonal to S).
  • the invention sets out to solve this problem by the method as characterised in claim 4, in which a method is defined for orienting particles having piezoelectric properties dispersed within a layer of material modifiable by an electromagnetic field to vary its electrical resistivity, from an insulator to a conductor or vice versa, characterized by striking the particles with a magnetic field to orient them.
  • a magnetic field enable to orient all the particles Qinv (see Fig. 1 to the right or Fig. 3 particles 90 to the left) in whatever orientation desired (Y axis), but this happens even at very low temperatures, e.g. maximum 150 °C, at which the substrate is still in a gelatinous form and not dry, and does not risk deterioration as a result of the high temperature.
  • the prior art instead, applying an electric field to a solid sandwich and not a fluid substrate, requires heating of the material to a high temperature, with consequent deterioration problems.
  • the axis X of the particles Qinv, 90 can be oriented at will simply by directing the magnetic field in the desired direction.
  • the particles Qinv, 90 are floating in the substrate 10 yet to solidify and rotate to orient themselves without much opposition.
  • the solution to orient the particles by a magnetic field can be used also for those containing PZT instead of quartz, with an improvement that is obtained by inserting into the particle structure (see fig. 2 particle 90) a layer of any ferromagnetic metal (with 1 to 4 free electrons).
  • the particle 90 is formed by an inner layer 60 of PZT, on which is placed a layer or component 54 of ferromagnetic metal, e.g. iron which is inexpensive.
  • the structure is placed between two outer electrically conductive layers 50, 64, e.g. of metal, e.g. silver.
  • the layer 54 e.g. also ferrite or cobalt-ferrite or a generic ferrous structure may be used.
  • the layers 50, 64 serve to collect the charges generated in the PZT or to lead an electrical signal to the particle 90.
  • the layer or component 54 can be inserted into the particle 90 after having built the layers 50, 60, 64 e.g. by diffusion in Edwards cell or by electronic bonding.
  • the particle 90 is preferably approximately a cube, e.g. having a side equal to 50 ⁇ m, optimally equal to 10-20 ⁇ m. Such thicknesses are well suited to be covered by thin layers of substrate 10 sprayed or laid with a brush.
  • the cube shape is obtained by cutting a wafer e.g. of 1cm x 1 cm x 50 ⁇ m.
  • the particle 90 in laboratory has provided about 140 pC/N 2 (on an area of 1/20 mm).
  • the magnetic field may be continuous, but if it is alternating, generated e.g. with an induction coil, at frequencies e.g. in the order of kHz, it is more advantageous because it periodically induces on the particles an orienting momentum, and period after period it can orient the quartz without stress on the material.
  • a method for orienting the said particles can be the following.
  • a magnetic field source 80 e.g. as that for the quartz
  • the axes of the particles 90 are varied to bring them from the configuration with Y axis to the one with X axis, in which the lying planes of the layers 50, 60, 64 are substantially (or nearly) parallel to the surface S.
  • a variation is to change the orientation of the axes Y when the substrate 10 is solidified or is solid.
  • the substrate 10 can be softened by heating, e.g. by means of a laser beam out of focus, and then operate with the source 80 as already said above. After removing the source that brings heat, the substrate 10 re-solidifies with the particles oriented inside.
  • the advantage of using a laser besides keeping cost limited, is the precision with which the area of softening is defined, thereby being able to intervene locally with desired resolution in the substrate 10.
  • the said substrate or matrix which contains all the dispersed elements which we will describe below may generically be a solvent, preferably aromatic.
  • a benzene is preferred, and preferably a dichlorobenzene (because it dissolves Thiophene well), a dichloromethane or a nitro type diluent.
  • a paint or substrate it is sufficient to use in general a substrate modifiable from the outside, e.g. via an electromagnetic field or laser, to vary its electrical resistivity, from an insulator to conductor or vice versa. In this way one can create conductive tracks inside the substrate to bring, transfer or receive signal (voltage or current) to said piezoelectric particles.
  • a further component such as e.g a graphite.
  • the graphites are excellent dopants, primarily for their high electrical conductivity. Peculiar graphite subfamilies which proved to be very advantageous, because said qualities are accentuated, are the fullerene and graphene.
  • the metal oxides may be:
  • Butadiene which has a very stable molecule.
  • Thiophene or polythiophene, which substitutes the vinyl.
  • the molecules of Thiophene have the marked characteristic, as will be seen later, of positioning themselves in a laminar manner, that is to say all on a plane without overlapping.
  • the sulphur atom of Thiophene has many electronic affinities with the matrix.
  • Thiophene has a free atom of Sulphur which acts as a binding agent among the monometric chains during polymerisation.
  • Thiophene and Butadiene can also be mixed together in the matrix.
  • the aforesaid polymers and graphites can co-operate together in the matrix with the metal oxides. Note however that one or more of said polymers may also be used alone in the matrix without the aid of the oxides and/or in their substitution (everything described for the rest of the substrate still applying).
  • Iron chloride or aluminium chloride may be added to the metal oxides plus the polymers or when they are alone to only one of the two.
  • Such chlorides are strong dopants, and are convenient both because they eliminate a hysteretic phenomenon which will be spoken of below and because they have a marked capacity to release/accept electrons.
  • the iron chloride or aluminium chloride are oxides dissolved in chlorine which dissolves well in thiophene, which is a plastic.
  • the excellent homogenisation ensures excellent communication at an electronic level, which favours the interchange of electrons towards the polymer (e.g. thiophene).
  • the metal oxides may, for example, consist of iron oxides in the formulation Fe 2 O 3 or Fe 3 O 4 or even better, for an improved magnetisation/ saturation curve, by chrome oxides or dioxides, in the formulation CrO 2 .
  • the metal oxides, with the optional graphite, and/or the optional polymers will be dispersed in the painting matrix or substrate.
  • the mixture of paint may be loaded with the metal oxides, or also with only one or several of said polymers, preferably Thiophene, and as said with some quartz (one or more of its 19 families), in particular BaTiO 3 or PbTiO 3 .
  • a component with TiO 3 has the advantage of being very gripping, does not dry and also is able to make free electrons available with little energy.
  • signals or current may be generated locally on the same paint or substrate or matrix by compressing it with a finger or any element or weight, or other system.
  • a laser beam there are created conductive tracks to collect from the electrodes of the particles QInv or 90 electrical signals, or to feed with the latter the electrodes.
  • quartz with greater granulometry to increase the substrate's conductivity.
  • quartz dispersed in the matrix in particular a thiophenic matrix, may constitute an obstacle to tracing the conductive tracks. In fact quartz does not conduct and a track would be interrupted.
  • This problem is solved by providing a layer of matrix with loaded quartz laid over a layer without it.
  • a first substrate composed as described is spread, then a second is spread over the first substrate when it has dried. Said particles of charged quartz are then dispersed in the second substrate, and they are given a specific spatial orientation where necessary. In the end the two layers appear as a single block.

Claims (15)

  1. Méthode pour insérer ou disperser des particules (P, 90) à propriétés piézoélectriques à l'intérieur d'un substrat (10), modifiable par un champ électromagnétique pour faire varier sa résistance électrique, d'isolant à conducteur ou inversement, caractérisé par le fait que
    sont dispersées dans le substrat des particules (P, 90) à structure sandwich composées de deux couches conductrices (E; 50, 64), de chaque côté d'une couche en matériau doté de propriétés piézoélectriques (Qinv,; 60).
  2. Méthode selon la proposition 1 dans laquelle, pour obtenir lesdites particules, on broie un matériau fritté à structure sandwich composé de deux couches conductrices (E) de part et d'autre d'une couche de quartz (Qinv).
  3. Méthode selon la proposition 1, dans lequel le matériau à propriétés piézoélectriques est le PZT.
  4. Méthode selon la proposition 1 ou 2 ou 3 dans laquelle
    on oriente les particules (P; 90) dispersées dans le substrat au moyen d'un champ magnétique.
  5. Méthode selon la proposition 1 ou 2 ou 3 ou 4, dans laquelle le champ magnétique est un champ magnétique alterné.
  6. Méthode selon l'une quelconque des propositions précédentes, dans laquelle on utilise un substrat (10) contenant un polymère à double liaison covalente conjuguée, c'est-à-dire un composé hétérocyclique constitué de n atomes de carbone et d'un atome d'un type différent, liés dans une structure en anneau.
  7. Méthode selon la proposition 6, comprenant comme polymère le Tiophène et/ou un polytiophène et/ou un Butadiène.
  8. Méthode selon l'une quelconque des propositions précédentes, dans laquelle
    - on étend un premier substrat, réalisé selon l'une quelconque des propositions précédentes,
    - on étend un second substrat, réalisé selon l'une quelconque des propositions précédentes, sur le premier substrat une fois que celui-ci est sec ;
    - On disperse dans le second substrat lesdites particules.
  9. Méthode selon l'une quelconque des propositions précédentes, dans laquelle on associe aux particules une couche de métal ferromagnétique.
  10. Composé comprenant
    - un substrat (10), et
    - une dispersion dans le substrat comprenant
    - un matériau capable de modifier ses propriétés, d'isolant à conducteur et inversement, lorsqu'il est heurté par un champ magnétique ou électromagnétique, et
    - des particules (P, 90) dotées de deux électrodes (E; 50, 64) et d'une couche intermédiaire d'un matériau doté de propriétés piézoélectriques (Qinv; 60) capable de donner ou recevoir des charges électriques à/depuis le substrat à l'effet piézoélectrique.
  11. Composé selon la proposition 10, dans lequel les axes géométriques (Y) passant par les électrodes desdites particules ont tous sensiblement la même orientation spatiale.
  12. Composé selon la proposition 11, dans lequel le substrat s'étend de manière prédominante le long d'une surface (S) et lesdits axes (Y) sont inclinés par rapport à l'orthogonale (H) à cette surface (S).
  13. Composé selon l'une quelconque des propositions de 10 à 12 comprenant un second substrat de solvant superposé au premier, le second substrat étant configuré selon l'une quelconque des propositions 10 à 13, mais sans lesdites particules.
  14. Composé selon l'une quelconque des propositions de 10 à 13, dans lequel le matériau à propriétés piézoélectriques est le PZT.
  15. Composé selon l'une quelconque des propositions de 10 à 15, dans lequel est associée aux particules une couche de métal ferromagnétique.
EP12797975.5A 2011-10-12 2012-10-09 Procédé permettant d'insérer ou de disperser des particules présentant des propriétés piézoélectriques à l'intérieur d'une couche Not-in-force EP2791985B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
PCT/IB2011/054507 WO2012137045A1 (fr) 2011-04-07 2011-10-12 Procédé ou méthode d'insertion ou d'étalement de quartz à l'intérieur d'un substrat
PCT/IB2011/055194 WO2012137048A1 (fr) 2011-04-07 2011-11-19 Composé destiné à produire des circuits conducteurs
PCT/IB2012/055455 WO2013054259A2 (fr) 2011-10-12 2012-10-09 Procédé permettant d'insérer ou de disperser des particules présentant des propriétés piézoélectriques à l'intérieur d'une couche

Publications (2)

Publication Number Publication Date
EP2791985A2 EP2791985A2 (fr) 2014-10-22
EP2791985B1 true EP2791985B1 (fr) 2018-02-28

Family

ID=48087096

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12797975.5A Not-in-force EP2791985B1 (fr) 2011-10-12 2012-10-09 Procédé permettant d'insérer ou de disperser des particules présentant des propriétés piézoélectriques à l'intérieur d'une couche

Country Status (5)

Country Link
US (1) US20140264142A1 (fr)
EP (1) EP2791985B1 (fr)
CN (1) CN104040745B (fr)
RU (1) RU2642884C2 (fr)
WO (1) WO2013054259A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3128609A1 (fr) * 2021-10-22 2023-04-28 Commissariat A L'energie Atomique Et Aux Energies Alternatives Dispositif piezoelectrique a fort coefficient piezoelectrique

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54120899A (en) * 1978-03-10 1979-09-19 Nippon Telegr & Teleph Corp <Ntt> Macromolecule complex piezo material
JPS6051750A (ja) * 1983-08-30 1985-03-23 Murata Mfg Co Ltd 防振複合体
US6191523B1 (en) * 1997-07-30 2001-02-20 The United States Of America As Represented By The Secretary Of The Navy Tranducing composite of sintered piezoelectric ceramic granules in a polymer matrix
US6473072B1 (en) * 1998-05-12 2002-10-29 E Ink Corporation Microencapsulated electrophoretic electrostatically-addressed media for drawing device applications
JP2006097087A (ja) * 2004-09-29 2006-04-13 Fuji Photo Film Co Ltd 成膜方法及び成膜装置
CN100466321C (zh) * 2006-12-22 2009-03-04 北京科技大学 一种制备巨磁电复合材料的电镀方法

Also Published As

Publication number Publication date
RU2642884C2 (ru) 2018-01-29
RU2014118827A (ru) 2015-11-20
CN104040745B (zh) 2016-12-07
WO2013054259A3 (fr) 2013-08-08
CN104040745A (zh) 2014-09-10
WO2013054259A2 (fr) 2013-04-18
EP2791985A2 (fr) 2014-10-22
US20140264142A1 (en) 2014-09-18

Similar Documents

Publication Publication Date Title
Baker et al. Size control of gold nanoparticles grown on polyaniline nanofibers for bistable memory devices
Martins et al. Polymer‐based magnetoelectric materials
US10236794B2 (en) Hybrid power generating device
EP1522082A2 (fr) Procede de stockage d&#39;energie electrique dans des batteries quantiques
WO2011125037A2 (fr) Procédé de production de circuits électriques sur une surface donnée
Banerjee et al. Piezoelectric and dielectric characterization of corona and contact poled PZT-epoxy-MWCNT bulk composites
Kushwah et al. Dielectric, pyroelectric and polarization behavior of polyvinylidene fluoride (PVDF)-gold nanoparticles (AuNPs) nanocomposites
EP2791985B1 (fr) Procédé permettant d&#39;insérer ou de disperser des particules présentant des propriétés piézoélectriques à l&#39;intérieur d&#39;une couche
Yu et al. Tuning the Energy Storage Efficiency in PVDF Nanocomposites Incorporated with Crumpled Core–Shell BaTiO3@ Graphene Oxide Nanoparticles
Sahu et al. Significant enhancement of dielectric properties of graphene oxide filled polyvinyl alcohol nanocomposites: Effect of ionic liquid and temperature
Yun et al. Piezoelectric Performance of Cubic‐Phase BaTiO3 Nanoparticles Vertically Aligned via Electric Field
Cai et al. Electrical transport in polyaniline–barium ferrite nanocomposites with negative giant magnetoresistance
Zhong et al. Polymer Nanocomposites for Dielectrics
Winter et al. Dielectrophoresis of non-spherical particles
Beck et al. An approach for transparent and electrically conducting coatings: A transparent plastic varnish with nanoparticulate magnetic additives
EP2695494A1 (fr) Procédé ou méthode d&#39;insertion ou d&#39;étalement de quartz à l&#39;intérieur d&#39;un substrat
US20170001388A1 (en) A body comprising a particle structure and method for making the same
EP2695495A1 (fr) Composé destiné à produire des circuits conducteurs
US6906909B2 (en) A C capacitor
Vijayakumar et al. Dielectric Properties of Polyvinylchloride (PVC) Composites and Nanocomposites
Cho et al. Polyepoxide-based nanohybrid films with self-assembled linear assemblies of nanodiamonds
Li et al. Dielectric behaviors of carbon nanotube/silicone elastomer composites
Stoyanov Soft nanocomposites with enhanced electromechanical response for dielectric elastomer actuators
Lima Magnetically responsive inks for printed electronics components and devices: integration into fully printed magnetic sensors
Che Dielectric polymer nanocomposites for energy storage

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140912

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20170926

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 975045

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180315

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012043437

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180228

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 975045

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180528

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180528

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180529

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012043437

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20181129

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20181031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181009

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181031

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181031

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181009

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181009

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180228

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20121009

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180628

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20201027

Year of fee payment: 9

Ref country code: GB

Payment date: 20201027

Year of fee payment: 9

Ref country code: FR

Payment date: 20201026

Year of fee payment: 9

Ref country code: DE

Payment date: 20201028

Year of fee payment: 9

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602012043437

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20211009

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211009

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220503

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211009